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In Part I of this series (I), the Mulliken electronegativity The equalized Mulliken electronegativity a., in a molecule
scale (2, 3) has been revised and extended to consider 50 or polyatomic ion may he calculated by (14,15)
elements. I t is shown that an alternate method of assign-
ment of "typical" singly bonded valence states to main
groups V-VII of the periodic table allows conversion of Mul-
liken electronegativities to the well-known Pauling units (4, where u represents the number of atoms of a particular
5) with unprecedented accuracy and solves a half-century- element in the species formula (e.g., for BFa-, U B = 1and UF
old puzzle concerning the physical dimensions of the two = 4) and q represents the net charge on the species (e.g., for
scales. BFI-, q = -1). The partial ionic charge on an atom A in the
In this work, some of the more important applications of species may he calculated by rewriting eq 2 as
Mulliken electronegativities to topics in chemical education
are discussed, problems within the Mulliken system are
identified (with suggestions for their solution where possi-
ble), and recommendations are made for future research.
Calculation of Partial ionic Charges on Combined Atoms
from Mulllken Eleclronegativities
Calculated partial ionic charges on combined atoms are Using BF4- as an example, assigning the valence states B
valuable aids in understanding and teaching periodic varia- (V = 3) = te and F (V = 1) = 14.3%s (I).
tions in chemical and physical properties (6-8).A method of
partial ionic charge calculation applicable to Mulliken elec-
tronegativities has developed from the Iczkowski-Margrave
atomic charge-energy function (9),as extended by Hinze,
Whitehead, and Jaffe (10). For multiple ionizations, the
relative energy E of an atom A is approximately a quadratic
function of the charge, 6 ~If. the energy of the neutral atom A
in a specified valence state is set a t zero, the energy of A+ is The partial ionic charges have been given to three decimal
places in this example merely to minimize round-off error.
the valence-state ionization potential, IPv,and the energy of
As discussed in the section concerning bond energy calcula-
A-is thenegative of thevalence-state electron affinity, EAv.
This gives tion, they are not accurate to this level.
Correlation ol Mulllken a and b Parameters and the
Principle of Hard and Sofl Aclds and Bases
A highly electronegative atom will usually have both a
Assuming the energy as defined by eq 1to be a continuous high valence-state ionization potential and a high valence-
and differentiable function of charge, state electron affinity. Thus, it is not surprising that "the
values of a and b for an element parallel each other" (11,12),
or that the ratio bla remains fairly constant for many ele-
ments (16). A correlation of the "typical" singly bonded
Iczkowski and Margrave (9) and Hinze, Whitehead, and valence states discussed in Part I of this series (1)gives
Jaffe (10) have equated d E ~ l d with
6 ~ electronegativity, con-
sidering the Mulliken definition (2,3) to he a special case of
eq 2, with 6~ = 0. Huheey (Sb, 11, 12) has suggested the Nalewajski (16) has reported bla = 1.52 f 0.22, from ground-
following notation: state ionization potentials and electron affinities for several
IP, + EA, elements.
a, = inherent electronegativity = XA(M)= (3) Substitution of eq 7 into eqs 5 and 6 gives
2
~XA(M)
b~= charge coefficient = -= IP,, - EA,
d6A
The calculation of partial ionic charges from the Mulliken
..
a and b Darameters is accomnlished throueh the ao~lication~~ ~
CsHs 1,. S
CHO lr. 5 , h
give
COCHs tr, tr, te, s bc = (1.20 + 0.17)a,lNc (17)
COOH tr, tr. ', s
CFs
CClo
CN
18. .
te. '
di, dl
In addition to beinga measure of hardness (25), the Mulli-
ken b parameters is an inverse measure of charge capacity,
the ability to donate or withdraw charge as a function of
te. -
SiHs te. s
SiFa electronegativity change. Groups are effective reservoirs of
NNN tr, di, h charge capacity, increasingly so with increasing Nc. Charge
NH.
NO
-.
tr. v
S capacity considerations explain interesting chemical differ-
ences between atoms and arouns. such as the abilitv of
NOn
NF2
..
tr, te
groups ro funct~onboth as hette; charge donors and accep-
NCO tr, di, tr tors than atoms of wnilar inherent elecrroneaativit\
- (8h,Rd,
NCS tr, di, tr 28).
pH2 S Equations 15 and 16 do not take group structure into
OH
OCI ..,. 5 account and predict that isomeric groups have the same
electronegativity, provided that all valence states remain the
',
OClO
OCiO? ...,te, .
16.7% s, '
20% r. '
same. This is in agreement with Sanderson's principle of
electronegativity equalization (6a, 70, 13) hut has caused
0CiO3
OBrO?
OIO*
.. .20% s.
some concern (11.12). If Sanderson's orincinle is valid. and
there is theoretick sipport that it is (i9-31j, then struetur-
ON0 allv denendent inductive effects. so imnortant in organic
0NOz chemistry, should probably not be interpreted as polar ef-
OCHs fects (charge effects operating through bonds), but as field
OCsHs effects (charge-distance effects operating directly through
OCHO space) (28).
OCOCH. '. tr. h, te. s Equations 3 and 4 may be combined to give
OCN '. di, dl
SH -, S 8.21 5.71 ZPv = oA + b,12 (18)
SCN ', di, dl 10.94 3.88 3.10 2.7118
(33), needs to be revised to accommodate our modern views 9. Ierkowski, R. P.:Margrave, J. L. J . Am. Chom. Soc. 1961,83,3647.
of the electronegativity concept: 10. Hinze,J.; Whitehead,M. A.:snd Jsffe,H. H.J . A m , Chsm.Soc. 1963.85,148.
n. Huheey, J. E. J. Phys Chem 1965.69.3284,
1. The word pourer implies a specific physical dimension, energy1 12. Huhely, J. E. J.Phys. Chem 1966.70.2086.
time. A better word is ability. 13. Sanderson, R. T. Science 1951.114.670.
14. Reed.J. L. J.Phvr. Cham. 1981.85.148.
2. The word atom should be replaced by the phrase atom or group. 15. ~~st&h,S.G. J . C ~ ~ ~ . E 1984,61,588.
~ U C .
16. Nalewajski. R. F. J. Phys Chem. 1985.89,2831.
3. Pauling's definition implies that different bonded atoms in a 17. Pearsun, R. G. J.Arn.Cham.Soc. 1963,85. 3533.
single chemical species have different electronegativities. Thus, 16. Pearson, R. G. J. Chzm. Edur. 1968.45.581.
it violates Sanderson's principle of electronegativityequalization 19. Peanon, R. G. J. Chem. Educ 1968.45.643.
(6a, 70,13). 20. Pearson, R. G. Hard and Soft Acids ond Boaer: Dowden, Hutchinson and Ross:
Stroudshurg, PA, 1973.
4. Pauling's definition excludes the noble gases, whose very high , . B. he ~ e w i a~ c i d - ~ o sConcepts:
21. ~ e n r e nW e A" Oueruialu: Wiiey: New York. 1980:
electronegativitiesindicate only their relative resistance to elec- pp 253-303.